ATBECHDE....FRGB..ITLILUNLSE......................UDIM360 - Ver 2.5 (21 Aug 1997) 2100000/00201225EUROPEAN PATENT SPECIFICATIONB119900704EP86302784.3198604151987012119881104enenen72648419850424US199007041990271986121719864619900704199027198905105 5B 41M 5/132 AdeFarbbildnergemischeenChromogenic mixturesfrMélanges chromogènesDE-A- 2 151 113DE-A- 2 402 384FR-A- 1 545 991FR-A- 2 117 101GB-A- 1 303 942GB-A- 2 014 629US-A- 3 525 630Brunea, Robert W.400 East River RoadGrand Island New York 14072USRaby, James M.4681 West Park DriveLewiston New York 14092USMOORE BUSINESS FORMS, INC.00201569P08/48/EP300 Lang BoulevardGrand Island New York 14072-1697USTownsend, Derek Thomaset al000368107 Addington RoadGB-West Wickham, Kent BR4 9BWGBATBECHDEFRGBITLILUNLSE19861230198652 Field of the Invention

The present invention relates to mixtures of chromogens that are especially useful as colour formers in carbonless copying systems.

Description of the Prior Art

Chromogenic mixtures that form "black" shades are highly desirable for use in pressure sensitive carbonless recording systems. "Black" images have superior reproduction characteristics when copied by xerographic processes.

Additionally, "black" images provide excellent contrast, readability and are similar in appearance to traditional typewritten copy. In the context of carbonless systems, the term "black" refers to shades that range from dark gray to black in appearance and that are characterized by approximately straight line absorption throughout the entire visible range, approximately 400-700 millimicrons. The traditional carbonless recording system includes a top sheet that is coated on its back surface ("CB") with a multitude of microcapsules containing a marking liquid and a bottom sheet coated on its front ("OF") with an acidic material, such as an acidic clay or a phenolic resin, that reacts with the normally colourless marking fluid upon rupture of the CB microcapsules to form an image on the CF. The marking fluid contained in the microcapsules coated on the CB is typically a mixture of chromogenic materials dissolved within a carrier oil or fluid.

Zinc-modified phenolic resins are now widely favoured as the acidic material coated on the CF. This is due to their high reactivity, stabilizing effect on the formed images with respect to light and dark exposure and their low abrasiveness on paper coating equipment. However, zinc-modified phenolic resins display an unexpected inability to synergistically react with many mixtures of two or more chromogens. Rather, most blends of chromogens when imaged on zinc-modified phenolic resins show antagonism with respect to the imaging properties of each other resulting in undesirable shades, poor intensity, or both. This antagonism problem is particularly evident in chromogenic blends intended to form "black" images.

To date, the traditional solution to this problem has been the use of so-called "single component black" precursors. These chromogens are generally blackish green coloured fluorans that are used alone or in combination with small amounts (5%-20% by weight) of toner chromogens in order to achieve a preferred "black" shade and to avoid the blending antagonism caused by zinc-modified phenolic resins. However, the use of "single component blacks" is undesirable from a commercial standpoint since they are generally quite expensive and must be applied in relatively large amounts. Thus, there is a need for a chromogenic mixture that will produce a "black" shaded image with zinc-modified phenolic resins while avoiding the antagonistic blending characteristics of such resins and at the same time eliminating or substantially reducing the amount of "single component black" chromogen used.

Most chromogenic mixtures include crystal violet lactone (3, 3-bis (p-dimethylamino phenyl), 6-dimethyl amino phthalide) as one of the chromogenic components. For example, U.S. Patents Nos. 4,376,150 (Morita et al.); 4,180,405 (Lawton); and 4,168,845 (Oeda et al.) all disclose chromogenic mixtures including, inter alia CVL and a green chromogen. U.S. Patents Nos. 4,363,664 (Delaney); 4,324,817 (Dahm et al.); 4,275,906 (Johnson et al.); 4,263,047 (Miyamoto et al.); 4,262,936 (Miyamoto); 4,197,346 (Stevens); 4,032,690 (Kohmura); 3,952,117 (Miyamoto); 3,940,275 (Brockett et al.); and 3,560,229 (Farnham et al.) all disclose chromogenic mixtures including, inter alia. CVL and various other fluoran homologs, isomers and analogs. These blends, however, suffer from antagonism problems when imaged on zinc-modified phenolic resins. In addition, the blends disclosed in the Brockett et al are blue, not black. U.S. Patents Nos. 3,857,675 (Schwab et al.) and 3,849,164 (Schwab et al.) both teach blends of essentially green and red chromogens to produce a "black" shade that avoid the use of CVL entirely. See also U.S. Patent No.4,073,614 (Ozutsumi et al).

From Specification GB-A 2 014 629, example 1, a substantially colourless but colourable marking liquid composition is known, said composition comprising an organic oil solution having a chromogenic mixture dissolved therein, the chromogenic mixture comprising

After developing with silton clay a stable black image is obtained.

Also from Specification FR-A 1 545 991, example 4, a chromogenic mixture is known, said mixture comprising

The mixture gives rise to a black colour on developing with clay.

SUMMARY OF THE INVENTION

It is the object of the present invention to provide an improved chromogenic mixture.

It is a further object of the present invention to provide a mixture of chromogens capable of forming a "black" shade when reacted with a zinc-modified phenolic resin in a carbonless copy system.

It is another object of the present invention to provide a substantially colourless marking liquid composition containing a mixture of chromogens dissolved in an organic oil that is capable of producing a "black" image when reacted with a zinc-modified phenolic resin in a carbonless copy system.

According to the present invention there is provided a chromogenic mixture for use in a carbonless copying system that includes at least three components the first component being a chromogen capable of being developed into a blue, indigo or violet colour that should be present in an amount of approximately 5% to 60% by weight, the second component being a chromogen capable of being developed into an orange colour that is present in the mixture in an amount of approximately 10% to 60% by weight characterised in that the mixture includes approximately 35% to 70% by weight of a chromogen capable of being developed into a green or single component black colour and in that the orange chromogen has the following formula: where R1, R2, and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof as that on development of the mixture with zinc modified phenolic resin in a carbonless copying system a "black" image is obtained.

BRIEF DESCRIPTION OF THE DRAWINGS

DESCRIPTION OF THE PREFERRED EMBODIMENTS

The orange chromogens that form a component of the inventive chromogenic mixture capable of being developed into an orange colour, alone or in combination, all have the following formula: where R1, R2 and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof. A most preferred orange chromogen has R1 and R3 as methyl groups and R2 as hydrogen. Its technical name is 6'-diethyl amino, 1',3'-dimethyl fluoran. Another preferred orange chromogen has R1 as methyl and R2 and R3 as hydrogen. Its technical name is 6'-diethyl amino, 3'-methyl fluoran. A third preferred orange chromogen has R2 as a tert-butyl group and R1 and R3 as hydrogen. Its technical name is 2'-t-butyl, 6'-diethyl amino fluoran. The orange chromogen should be present in the chromogenic mixture in an amount from approximately 10% to 60% based on the total weight of the chromogenic mixture. Most preferably the orange chromogen may be present in an amount from 24% to 35% by weight.

With respect to the chromogen capable of being developed into a blue, indigo or violet colour, three preferred candidates, which may be used alone or in combination, are crystal violet lactone, 6-dimethylamino, bis(3-dimethylaminophenyl, 1,3-dimethylamino-phenyl)phthalide and 1',3',6',8'-tetra-(dimethylamino-phenyl)phthalide. Most preferably, crystal violet lactone is used as the blue, indigo or violet chromogen since it is highly reactive, widely available and relatively low in cost. The blue, indigo or violet chromogen should be present in an amount of approximately 5% to 60% based on a total weight of the chromogenic mixture. Most preferably, the blue, indigo or violet chromogen may be present in an amount of approximately 10% to 20% by weight. With respect to the chromogen capable of being developed into a green or single component black colour that forms the third component of the inventive chromogenic mixture, there are four preferred compounds, which may be used alone or in combination. The first is a single component black chromogen, 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran. The second is a green chromogen, 2'(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran. These two chromogens are the most preferred green or single component black chromogens.

The third preferred chromogen is a green chromogen, 2'-(bis-phenyl methylamino), 4'-methyl, 6'-diethylamino fluoran.

The fourth chromogen is a single component black chromogen, 2'-phenylamino, 3'-methyl, 6'(N-methyl, N-cyclohexylamino) fluoran. The selected green or single component black chromogen may be present in the inventive chromogenic mixture in an amount of approximately 30% to 70% based on the total weight of the mixture. Most preferably, the selected green or single component black chromogen may be present in an amount from 45% to 60% by weight. To form the inventive chromogenic mixtures, one or more of the chromogens from each of the three classes is selected and the chromogens are mixed together in the indicated amounts. In the context of carbonless copy systems, the chromogenic mixtures will generally be dissolved in an appropriate organic oil vehicle that is then microencapsulated and coated as a CB. Any of the numerous organic solvents or oils generally known in the carbonless art may be used to make a colourless marking liquid composition with the inventive chromogenic mixtures, e.g. diisopropyl naptha- lene, diarylethane and diaryl methane.

EXAMPLE 1

A chromogenic mixture was prepared containing 35% 6'-diethyl amino, 1', 3'-dimethyl fluoran, 20% crystal violet lactone, and 45% 2' (N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran based on the total weight of the chromogenic mixture. This mixture was then dissolved in an appropriate organic solvent in an amount of approximately 7% by weight based on the total weight of the solution to form a colourless liquid marking composition. This marking composition was microencapsulated, coated on paper as a CB and then imaged against a CF coated with zinc-modified phenolic resin as the reactive acidic material. The absorbance values shown in Table 1 were obtained on the Bausch & Lomb Opacimeter and the Hunter colorimeter for the formed images.

The liquid marking composition also exhibited absorbance throughout the visible range, approximately 400 to 700 milli-microns, as shown in Figure 1.

EXAMPLE 2

A second chromogenic mixture was formed with 24% 6'-diethylamino, 1', 3'-dimethyl fluoran, 16% crystal violet lactone, and 60% 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran based on the total weight of the chromogenic mixture. This chromogenic mixture was then dissolved in an appropriate organic solvent to form a colorless liquid marking composition having approximately 6% chromogenic mixture based on the total weight of the solution. The solution was also microencapsulated, coated on paper as a CB and then imaged against a CF coated with zinc-modified phenolic resin to form "black" appearing images. The images yielded the values shown in Table 2 on the B & L Opacimeter and the Hunter Colorimeter.

As shown in Figure 2, the liquid marking composition showed absorbance throughout the visible range upon spectrophotometric analysis. Similar tests have been performed with 2'-t-butyl, 6'-diethyl amino fluoran and 6'-diethyl amino, 3'-methyl fluoran yielding similarly satisfactory results. Thus, the inventive chromogenic mixtures form "black" images of suitable commercial intensity when imaged against CF sheets coated with zinc-modified phenolic resins.

 1. A chromogenic mixture for use in a carbonless copying system comprising: (a) approximately 5% to 60% by weight of a chromogen capable of being developed into a blue, indigo or violet colour; and (b) approximately 10% to 60% by weight of a chromogen capable of being developed into an orange colour, characterised in that the mixture includes approximately 35% to 70% by weight of a chromogen capable of being developed into a green or single component black colour and in that the orange chromogen has the following formula: where R1, R2, and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof so that on development of the mixture with Zinc modified phenolic resin in a carbonless copying system a "black" image is obtained. 2. The chromogenic mixture according to claim 1, characterised in that the chromogen capable of being developed into a blue, indigo, or violet colour is selected from the group consisting of crystal violet lactone, 6-dimethylamino,bis(3-dimethyl-aminophenyl-1,3-dimethylaminophenyl)phthalide and 1',3',6',8' tetra (dimethylaminophenyl)phthalide. 3. The chromogenic mixture according to claim 1 or 2, characterised in that the chromogen capable of being developed into a green or single component black colour is selected from the group consisting of 2'-(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran; 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran; 2'-(bis-phenyl methylamino), 4'-methyl, 6'-diethylamino fluoran; and 2'-phenylamino, 3'-methyl, 6'(N-methyl,N-cyclohexylamino) fluoran. 4. The chromogenic mixture of claim 1, 2 or 3, characterised in that the chromogen capable of being developed into an orange colour has R1 and R3 methyl groups and R2 as hydrogen and is present in an amount of approximately 35% by weight; the blue, indigo or violet dye is crystal violet lactone and is present in an amount of approximately 20% by weight; and the green or single component black chromogen is 2'-(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran and is present in an amount of approximately 45% by weight. 5. The chromogenic mixture of claim 1, 2 or 3, characterised in that the chromogen capable of being developed into an orange colour has R1 and R3 as methyl groups and R2 has hydrogen and is present in an amount of approximately 24% by weight, the blue, indigo or violet chromogen is crystal violet lactone and is present in an amount of approximately 16% by weight, and the green or single component black chromogen is 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran and is present in an amount of approximately 60% by weight. 6. A substantially colourless but colourable marking liquid composition for use in a carbonless copying system comprising an organic oil solution having a chromogenic mixture dissolved therein, the chromogenic mixture comprising: (a) approximately 5% to 60% by weight of a chromogen capable of being developed into a blue, indigo or violet colour; and (b) approximately 10% to 60% by weight of a chromogen capable of being developed into an orange colour (c) characterised in that the mixture includes approximately 35% to 70% by weight of a chromogen capable of being developed into a green or single component black colour and in that the orange chromogen has the following formula: where R1, R2 and R3 are alkyl groups having 1-5 carbon atoms or hydrogen or combinations thereof so that on development of the mixture with Zinc modified phenolic resin in a carbonless copying system a "black" image is obtained. 7. The marking liquid composition according to claim 6, characterised in that the chromogen capable of being developed into the blue, indigo or violet colour is selected from the group consisting of crystal violet lactone, 6-dimethylamino, bis(3-dimethylaminophenyl), 1,3-dimethylamino-phenyl phthalide and 1 ',3',6',8' tetra(dimethylaminophenyl)phthalide. 8. The marking liquid composition according to claim 6 or 7, characterised in that the chromogen capable of being developed into the green or single component black colour is selected from the group consisting of 2'-(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran; 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran; 2'-(bisphenyl methyl-amino), 4'-methyl, 6'-diethylamino fluoran; and 2'-phenyl-amino, 3'-methyl, 6'-(N-methyl, N-cyclohexylamino) fluoran. 9. The marking liquid composition according to claim 6, 7 or 8, characterised in that the chromogen capable of being developed into the orange colour has R1 and R3 as methyl groups and R2 as hydrogen and is present in an amount of approximately 35% by weight, the blue, indigo or violet dye is crystal violet lactone and is present in an amount of approximately 20% by weight; and the green or single component black chromogen is 2'-(N-methyl, N-phenylamino), 6'-(N-ethyl, N-p-tolylamino) fluoran and is present in an amount of approximately 45% by weight. 10. The marking liquid composition according to claim 6, 7 or 8, characterised in that the chromogen capable of being developed into the orange colour has R1 and R3 as methyl groups and R2 as hydrogen and is present in an amount of approximately 24% by weight; the blue, indigo or violet chromogen is crystal violet lactone and is present in an amount of approximately 16% by weight; and the green or single component black chromogen is 2'-(phenylamino), 3'-methyl, 6'-(N-ethyl, N-p-tolylamino) fluoran and is present in an amount of approximately 60% by weight. 1. Chromophorgemisch für kohlenstoffloses Kopiersystem enthaltend: (a) etwa 5 bis 60 Gew.-% eines Chromophoren, der zu blau, indigo oder violett entwickelbar ist und (b) etwa 10 bis 60 Gew.-% eines Chromophoren, der zu orange entwickelbar ist, dadurch gekennzeichnet, daß das Gemisch etwa 35 bis 70 Gew.-% eines Chromophoren enthält, der zu grün entwickelbar ist, oder Einkomponenten-schwarz ergibt und der orange-Chromophor der Formel entspricht, worin R1, R2 und R3 Alkylgruppen mit 1 bis 5 Kohlenstoffatomen und/oder Wasserstoff bedeuten, so daß man bei Entwicklung des Gemischs mit zinkmodifiziertem Phenolharz in einem kohlenstofffreien Kopiersystem ein "schwarzes" Bild erhält. 2. Chromophorgemisch nach Anspruch 1, dessen Chromophor, der zu blau, indigo oder violett entwickelbar ist, ein Kristallviolett-Lacton, 6-Dimethylamino-bis(3-dimethylaminophenyl-1,3-dimethylamino-phenyl)phthalid und/oder 1',3',6',8?etra(dimethylaminophenyl)phthalid ist. 3. Chromophorgemisch nach Anspruch 1 oder 2, wobei der Chromophor, der zu grün oder Einkomponenten-schwarz entwickelbar ist, ausgewählt ist aus 2'-(N-Methyi-N-phenyiamino)-6'-(N-ethyi-N-p-tolylamino)fluoran, 2'-(Phenylamino)-3'-methyl-6'-(N-ethyl-N-p-tolylamino)fluoran, 2'-(bis-Phenylmethyl- amino)-4'-methyl-6'-diethylaminofluoran und 2'-Phenylamino-3'-methyl-6'-(N-methyl-N-cyclohexylamino)fluoran. 4. Chromophorgemisch nach Anspruch 1, 2 oder 3, wobei in dem orange entwickelbaren Chromophoren R1 und R3 Methylgruppen und R2 ein Wasserstoffatom sind und in dem Gemisch in einer Menge von etwa 35 Gew.-% vorliegt, der Farbstoff für blau, indigo oder violett Kristallviolett-Lacton ist und in dem Gemisch in einer Menge von etwa 20 Gew.-% vorliegt und der Chromophor für grün oder Einkomponenten-schwarz 2'-(N-Methyl-N-phenylamino)-6'-(N-ethyl-N-p-tolylamino)fluoran ist und in einer Menge von etwa 45 Gew.-% enthalten ist. 5. Chromophorgemisch nach Anspruch 1, 2 oder 3, dessen orange entwickelbarer Chromophor als Substituent R1 und R3 Methylgruppen und als R2 ein Wasserstoffatom enthält und in einer Menge von etwa 24 Gew.-%, der Chromophor für blau, indigo oder violett Kristallviolett-Lacton ist und in einer Menge von etwa 16 Gew.-% und der Chromophor für grün oder Einkomponenten-schwarz 2'-(Phenylamino)-3'-methyl-6'-(N-ethyl-N-p-tolylamino)fluoran ist und in einer Menge von etwa 60 Gew.-% enthalten ist. 6. Eine im wesentlichen farblose, jedoch färbbare Markierungsflüssigkeit für kohlenstofflose Kopiersysteme, enthaltend eine Lösung eines Chromophorgemischs in einem organischen Öl, wobei das Chromophorgemisch folgende Komponenten enthält: (a) etwa 5 bis 60 Gew.-% eines zu blau, indigo oder violett färbbaren Chromophoren und (b) etwa 10 bis 60 Gew.-% eines zu orange färbbaren Chromophoren, dadurch gekennzeichnet, daß es (c) etwa 35 bis 70 Gew.-% eines zu grün entwickelbaren oder als Einkomponenten-schwarz Chromophor enthält und der zu orange entwickelbare Chromophor der Formel entspricht, worin R1, R2 und R3 Alkylgruppen mit 1 bis 5 Kohlenstoffatomen und/oder ein Wasserstoffatom bedeuten, so daß man bei der Entwicklung des Gemischs mit zinkmodifiziertem Phenolharz in einem kohlenstofffreien Kopiersystem ein "schwarzes" Bild erhält. 7. Markierflüssigkeit nach Anspruch 6, wobei der zu blau, indigo oder violett entwickelbare Chromophor Kristallviolett-Lacton, 6-Dimethylamino-bis(3-dimethylaminophenyl-1,3-dimethylaminophenyl)-phthalid und/oder 1',3',6',8'Tetra(dimethylaminophenyl)phthalid ist. 8. Markierflüssigkeit nach Anspruch 6 oder 7, wobei der zu grün entwickelbare oder Einkomponenten-schwarz Chromophor ausgewählt ist aus 2'-(N-Methyl-N-phenylamino)-6'-(N-ethyl-N-p-tolylamino)fluoran, 2'-(Phenylamino)-3'-methyl-6'-(N-ethyl-N-p-tolylamino)fluoran, 2'-(bis-Phenylmethylami- no)-4'-methyl-6'-diethylaminofluoran und 2'-phenylamino-3'-methyl-6'-(N-methyl-N-cyclohexylamino)-fluoran. 9. Markierflüssigkeit nach Anspruch 6, 7 oder 8, wobei in dem orange entwickelbaren Chromophoren R1 und R3 Methylgruppen und R2 ein Wasserstoffatom sind und er in dem Gemisch in einer Menge von etwa 35 Gew.-% vorliegt, der Farbstoff für blau, indigo oder violett Kristallviolett-Lacton ist und er in dem Gemisch in einer Menge von etwa 20 Gew.-% vorliegt und der Chromophor für grün oder Einkomponenten-schwarz 2'-(N-Methyl-N-phenylamino)-6'-(N-ethyl-N-p-tolylamino)fluoran ist und er in einer Menge von etwa 45 Gew.-% enthalten ist. 10. Markierflüssigkeit nach Anspruch 6, 7 oder 8, wobei dessen orange entwickelbarer Chromophor als Substituent R1 und R3 Methylgruppen und als R2 ein Wasserstoffatom enthält und er in einer Menge von etwa 24 Gew.-%, der Chromophor für blau, indigo oder violett Kristallviolett-Lacton ist und er in einer Menge von etwa 16 Gew.-% und der Chromophor für grün oder Einkomponentenschwarz 2'-(Phenylamino)-3'-methyl-6'-(N-ethyl-N-p-tolylamino)fluoran ist und er in einer Menge von etwa 60 Gew.-% enthalten ist. 1. Un mélange chromogène à utiliser dans un système de duplication sans carbone, comprenant: (a) environ 5% à 60% en poids d'un composant chromogène susceptible d'être développé en une couleur bleue, indigo ou violette; et (b) environ 10% à 60% en poids d'un composant chromogène susceptible d'être développé en une couleur orangée, caractérisé en ce que le mélange contient environ 35% à 70% en poids d'un composant chromogène susceptible d'être développé en une couleur verte, ou noire à un seul composant, et en ce que le composant chromogène orangé répond à la formule suivante: où R1, R2 et R3 sont des groupes alkyles comptant 1 à 5 atomes de carbone ou l'hydrogène ou des combinaisons d'entre eux, de sorte qu'une image "noire" soit obtenue par développement du mélange par une résine phénolique modifiée par du zinc dans un système de duplication sans carbone. 2. Le mélange chromogène selon la revendication 1, caractérisé en ce que le composant chromogène susceptible d'être développé en une couleur bleue, indigo ou violette est choisi dans le groupe formé par la lactone de violet cristallisé, le 6-diméthylamino-bis(3-diméthylaminophényl-1,3-diméthylaminophé- nyl)phtalide et le 1',3',6',8'-tétra(diméthylaminophényl)phtalide. 3. Le mélange chromogène selon la revendication 1 ou 2, caractérisé en ce que le composant chromogène susceptible d'être développé en une couleur verte, ou noire à un seul composant, est choisi dans le groupe formé par le 2'-(N-méthyl-N-phénylamino)-6'-(N-éthyl-N-p-tolylamino)fluoranne, le 2'-(phénylamino)-3'-méthyl-6'-(N-éthyl-N-p-tolylamino)fluoranne, le 2'-(diphénylméthylamino)-4'-méthyl-6'-diéthylamino-fluoranne et le 2'-phénylamino-3'-méthyl-6'-(N-méthyl-N-cyclohexylamino)fluoranne. 4. Le mélange chromogène de la revendication 1, 2 ou 3, caractérisé en ce que le composant chromogène susceptible d'être développé en une couleur orangée comporte des groupes méthyle en tant que R1 et R3 et de l'hydrogène en tant que R2 et il est présent en une quantité d'environ 35% en poids; le colorant bleu, indigo ou violet est la lactone de violet cristallisé et il est présent en une quantité d'environ 20% en poids; et le composant chromogène vert, ou noir à un seul composant, est le 2'-(N-méthyl-N-phé- nylamino)-6'-(N-éthyl-N-p-tolylamino)fluoranne et il est présent en une quantité d'environ 45% en poids. 5. Le mélange chromogène de la revendication 1, 2 ou 3, caractérisé en ce que le composant chromogène susceptible d'être développé en une couleur orangée comporte des groupes méthyle en tant que R1 et R3 et de l'hydrogène en tant que R2 et il est. présent en une quantité d'environ 24% en poids; le composant chromogène bleu, indigo ou violet est la lactone de violet cristallisé et il est présent en une quantité d'environ 16% en poids; et 'le composant chromogène vert, ou noir à un seul composant, est le 2'-(phénylamino)-3'-méthyl-6'-(N-éthyl-N-p-tolylamino)fluoranne et il est présent en une quantité d'environ 60% en poids. 6. Une composition de liquide de marquage sensiblement incolore mais capable de prendre une couleur, à utiliser dans un système de duplication sans carbone, comprenant une solution à base d'huile. organique dans laquelle est dissous un mélange chromogène, le mélange chromogène comprenant: (a) environ 5% à 60% en poids d'un composant chromogène susceptible d'être développé en une couleur bleue, indigo ou violette; et (b) environ 10% à 60% en poids d'un composant chromogène susceptible d'être développé en une couleur orangée (c) caractérisé en ce que le mélange contient environ 35% à 70% en poids d'un composant chromogène susceptible d'être développé en une couleur verte, ou noire à un seul composant, et en ce que le composant chromogène orangé répond à la formule suivante: où R1, R2 et R3 sont des groupes alkyles comptant 1 à 5 atomes de carbone, ou l'hydrogène ou des combinaisons d'entre eux, de sorte qu'une image "noire" soit obtenue par développement du mélange par une résine phénolique modifiée par du zinc dans un système de duplication sans carbone. 7. La composition de liquide de marquage selon la revendication 6, caractérisée en ce que le composant chromogène susceptible d'être développé en une couleur bleue, indigo ou violette est choisi dans le groupe formé par la lactone de violet cristallisé, le 6-diméthylamino-bis(3-diméthylaminophényl)-1,3-dimé- thylaminophényl-phtalide et le 1',3',6',8'-tétra(diméthylaminophényl)phtalide. 8. La composition de liquide de marquage selon la revendication 6 ou 7, caractérisée en ce que le composant chromogène susceptible d'être développé en la couleur verte, ou noire à un seul composant, est choisi dans le groupe formé par le 2'-(N-méthyl-N-phénylamino)-6'-(N-éthyl-N-p-tolylamino)fluoranne, le 2'-(phénylamino)-3'-méthyl-6'-(N-éthyl-N-p-tolylamino)fluoranne, le 2'-(diphényi- méthylamino)-4'-méthyl-6'-diéthylamino-fluoranne et le 2'-phénylamino-3'-méthyl-6'-(N-méthyl-N-cyclohexylamino)fluoranne. 9. La composition de liquide de marquage selon la revendication 6, 7 ou 8, caractérisée en ce que le composant chromogène susceptible d'être développé en la couleur orangée comporte des groupes méthyle en tant que R1 et R3 et de l'hydrogène en tant que R2 et il est présent en une quantité d'environ 35% en poids; le colorant bleu, indigo ou violet est la lactone de violet cristallisé et il est présent en une quantité d'environ 20% en poids; et le composant chromogène vert, ou noir à un seul composant, est le 2'-(N-méthyl-N-phénylamino)-6'-(N-éthyl-N-p-tolylamino)fluoranne et il est présent en une quantité d'environ 45% en poids. 10. La composition de liquide de marquage selon la revendication 6, 7 ou 8, caractérisée en ce que le composant chromogène susceptible d'être développé en la couleur orangée comporte des groupes méthyle en tant que R1 et R3 et de l'hydrogène en tant que R2 et il est présent en une quantité d'environ 24% en poids; le composant chromogène bleu, indigo ou violet est la lactone de violet cristallisé et il est présent en une quantité d'environ 16% en poids; et le composant chromogène vert, ou noir à un seul composant, est le 2'-(phénylamino)-3'-méthyl-6'-(N-éthyl-N-p-tolylamino)fluoranne et il est présent en une quantité d'environ 60% en poids.